Dyestuffs of the anthraquinone series



Patented July 4%, 1944 TE T nizns'ruresoe THE ANTHRAQUINQNE SERIES T s. n n ie ri l es a L t e -pr ae lq @Q n y fis o th e thmqa nenev-s ieszemi more pa i ly q prepara ion o aci W001 dyestufisi-whi-clr dye 'in-ga yarietyefshades; and

.f' 'Inthe'dyesiof the anthraquinone'acid woolzdye stuff series there'ar'efknown thoseawhich are;pre,- pared by'ithe condensation of -l amino= iranilinq anthraqdinonee2=sulfoniciacid with formaldehyde under conditions which "give ardi -molecular: c'on' densation product in which it is presumed; that diph'enyrmethan'e formsithe connecting linkh lt is ailso knownthat' simiiar dyes may be produced by condensing"l aznino i broniofl-anthraquinone sulfonic" acidswith 4,4fi-diafnino-diphenyr math 1 i tt of .nianiie jii deasimp ew M i V .o anni dyesoi the ary am cqanthra meatless which the ali i ids pntlcom ritestgdi-L. phenyl methanenu'cIeU's', and in'which the di phenyl methane nucleus may be symmetrically 0r unsymmetrically substituted by aryl radicals comprising at least one anthraquinonylamino group.

According to the present invention an anilino anthraqninone compound which carries in the para position of the anilino group a methylol radical is condensed with substituted arylamines in which at least one aryl group is of the benzene series and has the position para to the amine group unsubstituted. The condensation is effected by warming the reacting compounds together in an aqueous acid medium, such as with diluted hydrochloric, sulfuric, and acetic acids, etc.

The following examples are given to illustrate the invention. The parts used are by weight.

lication SerialNo. 362 626 Q I "Wilmington, DeL, assignor t0 flflil tfi' iblbmpu rs & Company, "Wilming- M apex-parat ion of Delaware" Octbber 24, i940,

Mix intimately ten pasts-erhexane-tannins 2.-anthraquinone sodium sulfonate, and 10 parts of 1-amino-4-p-methylol aiiilino 2 anthraquinone sodium-sulfonata'and add1to 180 parts 'of sulfuric acid: Heat to.60 C: and liold'for 4 hours. Filter the suspension 'and wash-with 60% sulfuridacid: Dissolve the'cake in 500 partsof Water and salt to 14%-so'diuin chloride: Theiso-y lated' dyestufffisiessentially" .7 r'

' If b e e. H H and dyes Wool blue shades, fast to fulling and washings" MN I 1 Exdmplez Dissolve in'ZOOpaIt s of water;4'.46 parts of 1- a min 0 4-p-methy1ol-anilinoe' arithraduinon sulfonate of sodium, 3.75 parts er Metahil Yellow and addf2f'parts of eiaeiaiieceuc "acid. for one hour, and'saltto La 4% salt solution. .006] and decant 'thelinother liduoi' fi' OYn the precipitated .onyc'ompdund... Stir the-residue with 200 parts of alcohol smelter, Wash 'With alcoholand dry. s isa. green dyestufi having fg'ood 17TH; NH: c Of/Qsmm NaOaS- 11 H l 0 EN NH 0 N02 It dyes wool blue-green shades having good fastness to washing and fulling.

Example 4 Add 4.46 parts of 1-amino-4-(p-methy1ol-anilino) -2-anthraquinone sodium sulfonate, and 4.17 parts of 1-hydroxy-4-anilino-2-anthraquinone sodium sulfonate, to 200 parts of water. Add 2 parts of glacial acetic acid. Reflux four hours. Cool the mass and filter oil the crystalline pre cipitate and wash and dry the filter cake.

The product is presumed to have the formula,

NH2 OH (H) II I OiIj-soma Naois A C NH O H It dyes wool reddish-blue shades of good fastness to fulling and washing. r

V Example 5 0 EN 0 NH dyes in blue shades.

I have found the para-methylol-anilino group to be quite reactive when contacted with an anilino group which carries a labile hydrogen atom. Any'diarylamine in which one aryl group is of the benzene series andthe position in such benzene ring para to the amine group is unsubstituted may be condensed with the methylol group "of the arylaminoanthraquinone. Neither the p-methylolanilinoanthraquinone nor the diarylamine with which it is condensed need contain a sulfonic acid radical prior to condensation. Where at least one of the anthraquinone groups does not contain a sulfonic acid group the product may be rendered water soluble by sulfonation under the conditions usually employed in sulfonating arylaminoanthraquinones. The arylaminoanthraquinones which carry the sulfonic acid group in the anthraqninone nucleus in other than the 2-position may be substituted for the particular compounds mentioned in the examples to give acid wool dyes of this series.

This process makes possible the preparation of dyes of a wide variety of shades and dyeing properties by varying the second component that goes to make up the molecule. The dimolecular structure in acid wool dyes of this series is found to impart desirable fastness properties, particularly to washing and fulling.

I claim: i

1. The process for preparing arylaminoanthraquinone compounds in which the arylamino radical is an amino-diphenyl-methane group, which comprises reacting in aqueous acid medium upon an anilinoanthraquinone which carries a methylol group in the para position of the anilino radical, with a diarylamine in which one aryl group is of the benzene series and is unsubstituted in the position para to the amine group.

2. The process for preparing arylaminoanthraquinone compounds in which the arylamino radical is an amino-diphenyl-methane group, which comprises reacting in aqueous acid medium upon an anilinoanthraquinone which carries a methyl- 01 group in the para position of the anilino radical, with an anilinoanthraquinone in which the anilino radical is unsubstituted in the para position. s

' 3. The process for preparing. arylaminoanthraquinone sulfonic acids in which the arylamino radical is an amino-diphenyl-methane, group, which comprises reacting in aqueous acid medium upon an anilinoanthraquinone sulfonic acid which carries a methylol group in the para position of the anilino radical, with a diarylamine in which one aryl group isof the benzene series and is unsubstituted in the position para tothe amine,

p- 4. The process for preparing arylaminoanthraquinone sulfonic acids in which thearylami o radical is an amino-diphenyl-methane I group, which comprises reacting in aqueous acidmedium upon an anilinothraquinone sulfoni c= acid which carries a methylol group in'the para position of the anilino radical, with an anilinoanthraquinone in which the anilino radical is unsubstituted in 

